Catalyst composition to effect metathesis of acetylenes

ABSTRACT

Tungsten compounds of the formula: 
     
         [L.sub.Y X.sub.n+3 W.tbd.CR.sup.3 ].sup.n- (M.sup.+).sup.n 
    
     wherein 
     R 3  is an alkyl or aryl; 
     L is a moiety of the formula ZR 4  R 5  R 6 , (O)ZR 4  R 5  R 6 , ZR 4  R 5  (OR 6 ), ZR 4  (OR 5 ) (OR 6 ) or Z(OR 4 ) (OR 5 ) (OR 6 ); wherein Z is a group 5 element including N, P or As and R 4 , R 5  and R 6  can be the same or different and are alkyl, aralkyl or aryl; 
     X is F, Cl, Br, I, OR 4 , NR 4  R 5  or SR 4  ; 
     M +  is a metallic or organic cation; alkyl has 1-10 carbons, aralkyl has 7-10 carbons and aryl has 6-10 carbons; 
     n is 0 or 1, and y is 0, 1 or 2, with the proviso that: 
     y is 0 when X is OR 4 , NR 4  R 5  or SR 4 , and n=0; 
     y is 0 when X is OR 4 , F, Cl, Br or I, and n=1. 
     These compounds will transform unsymmetric acetylenes into a mixture containing the unsymmetric acetylene and the two possible symmetric acetylenes in their thermodynamically determined relative amounts at equilibrium. The equilibrium can involve any number of acetylenes and can be reached from any point off equilibrium.

The Government has rights in this invention pursuant to Grant No. CHE 79 05307 awarded by the National Science Foundation.

BACKGROUND OF THE INVENTION

The invention relates to homogeneous catalysts for the metathesis of acetylenes (alkynes), a process which is defined as the redistribution of alkylidyne moieties in a mixture of alkynes.

For example,

    2XR'C.tbd.CR.sup.2 ⃡R'C.tbd.CR'+R.sup.2 C.tbd.CR.sup.2.

Prior to the present invention, there has been no report of a homogeneous tungsten catalyst for the metathesis of alkynes. Two types of alkyne metathesis catalysts are known, heterogeneous catalysts containing tungsten which operate inefficiently at 300°-400° C. (F. Pannella, R. L. Banks and G. C. Bailey, J. Chem. Soc. Chem. Comm., 1548 (1968)), and a homogeneous catalyst system made from Mo(CO)₆ and phenol in toluene (A. Mortreux, J. C. Delgrange, M. Blanchard and B. Lubonchinsky, J. Molec. Catal. 2, 73 (1977); S. Devarajan, O. R. M. Walton and G. J. Leigh, J. Organometal. Chem., 181, 99 (1979)). None of the prior art has identified the catalytically active species or site.

It would be desirable to provide a homogeneous catalyst for the metathesis of acetylenes because it, like olefin metathesis, allows manipulation of hydrocarbon feedstocks in the chemical industry.

SUMMARY OF THE INVENTION

The compounds of the present invention have the general formula:

    [L.sub.Y X.sub.n+3 W.tbd.CR.sup.3 ].sup.n- (M.sup.+).sup.n

wherein

R³ is an alkyl or aryl;

L is a moiety of the formula ZR⁴ R⁵ R⁶, (O)ZR⁴ R⁵ R⁶, ZR⁴ R⁵ (OR⁶), ZR⁴ (OR⁵) (OR⁶) or Z(OR⁴) (OR⁵) (OR⁶), wherein Z is a group 5 element including N, P or As and R⁴, R⁵ and R⁶ can be the same or different and are alkyl, aralkyl or aryl;

X is F, Cl, Br, I, OR⁴, NR⁴ R⁵ or SR⁴ ;

M⁺ is a metallic or organic cation; alkyl has 1-10 carbons, aralkyl has 7-10 carbons and aryl has 6-10 carbons;

n is 0 or 1 and y is 0, 1 or 2, with the proviso that:

y is 0 when X is OR⁴, NR⁴ R⁵ or SR⁴, and n=0;

y is 0 when X is OR⁴, F, Cl, Br or I, and n=1.

Examples of alkyl groups are methyl, ethyl, isopropyl, t-butyl, hexyl, octyl, decyl and neopentyl.

Examples of arylkyl groups are benzyl, p-ethylbenzyl, naphthylmethyl and diphenylmethyl.

The terms "aryl" and "ar" are employed here to denote a radical derived from a hydrocarbon, having as its only unsaturation aromatic unsaturation in six membered carbocyclic rings, by removal of a hydrogen atom from a nuclear carbon atom of an aromatic ring. Examples of aryl groups are phenyl, 1- and 2-naphthyl, o-, m-, and p-tolyl, ethylphenyl, butylphenyl, xylyl and trimethylphenyl.

Examples of M⁺ are [NR³ R⁴ R⁵ R⁶ ]⁺, [PR³ R⁴ R⁵ R⁶ ]⁺, Li⁺, K⁺ or Na⁺, preferably NEt₄ ⁺, NMe₄ ⁺ or PMe₄ ⁺.

When X is F, Cl, Br or I, the compounds of this invention where y is 0 are prepared in accordance with reactions 1 or 2 ##STR1##

    (Me.sub.3 CCH.sub.2).sub.3 W.tbd.CCMe.sub.3 +3HX+MX→3CMe.sub.4 +[X.sub.4 W.tbd.CCMe.sub.3 ].sup.- M.sup.+                ( 2)

(Me=CH₃); a typical solvent is diethyl ether, tetrahydrofuran, chlorobenzene or dichloromethane and a typical temperature is between about -78° C. and 50° C., preferably about 25° C. The product is recovered by filtration or by removing the solvent in vacuo. Two compounds of this invention which are prepared in accordance with reactions 1 and 2 are shown in equations 3 and 4 (Et=C₂ H₅).

    (Me.sub.3 CCH.sub.2).sub.3 W.tbd.CCMe.sub.3 +3HCl→3CMe.sub.4 +Cl.sub.3 W.tbd.CCMe.sub.3                                ( 3)

    (Me.sub.3 CCH.sub.2).sub.3 W.tbd.CCMe.sub.3 +3HCl+NEt.sub.4.sup.+ Cl.sup.- →3CMe.sub.4 +[Cl.sub.4 W.tbd.CCMe.sub.3 ].sup.- NEt.sub.4.sup.+( 4)

Reactions 3 and 4 can be conducted in ether solvent at a temperature between about -78° C. and 25° C. The product is recovered by filtration.

Compounds in which X is Cl or Br and which contain L are prepared in accordance with reaction 5. Two compounds of this

    [X.sub.n+3 W.tbd.CCMe.sub.3 ].sup.n- +.sub.Y L→nx.sup.- +L.sub.Y X.sub.3 W.tbd.CCMe.sub.3                                  ( 5)

invention which are prepared in accordance with reaction 5 are shown in equations 6 and 7.

    [Cl.sub.4 W.tbd.CCMe.sub.3 ].sup.- +3PMe.sub.3 →Cl.sup.- +Cl.sub.3 (PMe.sub.3).sub.3 W.tbd.CCMe.sub.3                        ( 6)

    [Cl.sub.4 W.tbd.CCMe.sub.3 ].sup.- +(O)PMe.sub.3 →Cl.sup.- +Cl.sub.3 [(O)PMe.sub.3 ]W.tbd.CCMe.sub.3                           ( 7)

These reactions can be conducted in a tetrahydrofuran or toluene solvent at a temperature between about -78° C. and 25° C. The product is recovered by filtration.

Compounds in which X is OR⁴, NR⁴ R⁵ or SR⁴ are prepared as shown in equation 8. Preparation of a typical compound of this

    [Cl.sub.4 W.tbd.CCMe.sub.3 ].sup.- +3MX→Cl.sup.- +3MCl+X.sub.3 W.tbd.CCMe.sub.3                                          ( 8)

invention is shown in equation 9.

    [Cl.sub.4 W.tbd.CCMe.sub.3 ].sup.- +3LiOCMe.sub.3 →Cl.sup.- +3LiCl+(Me.sub.3 CO).sub.3 W.tbd.CCMe.sub.3               ( 9)

Reaction 9 can be conducted in tetrahydrofuran solvent at a temperature between about -78° C. and 25° C. The product is recovered by sublimation.

Compounds of this invention in which R³ is t-butyl can be prepared by the reaction shown in equation 10 where 1 is 4

    [L.sub.Y X.sub.n+3 W.tbd.CR.sup.3 ].sup.n- (M.sup.+).sup.n +R.sup.4 C.tbd.CR.sup.5 →R.sup.1 C.tbd.CCMe.sub.3 +[L.sub.Y X.sub.n+3 W.tbd.CR.sup.m ].sup.n- (M.sup.+).sup.n                   ( 10)

if m is 5, and vice versa, or R⁴ and R⁵ are identical. Typical compounds of this invention which can be prepared in accordance with reaction 10 can be prepared as shown in reactions 11 and 12

    Cl.sub.3 (PMe.sub.3).sub.3 W.tbd.CCMe.sub.3 +PhC.tbd.CPh→PhC.tbd.CCMe.sub.3 +Cl.sub.3 (PMe.sub.3).sub.3 W.tbd.CPh                                                 (11)

    (Me.sub.3 CO).sub.3 W.tbd.CCMe.sub.3 +EtC.tbd.CEt→EtC.tbd.CCME.sub.3 +(Me.sub.3 CO).sub.3 W.tbd.CEt                            (12)

(Ph is phenyl).

The reactions shown in equations 10, 11 and 12 constitutute alkyne metathesis when one or more alkynes are present in excess as shown in equations 13 and 14 (all ligands except .tbd.CR

    W.tbd.CR.sup.5 +R.sup.4 C.tbd.CR.sup.5 →W.tbd.CR.sup.4 +R.sup.5 C.tbd.CR.sup.5                                            ( 13)

    W.tbd.CR.sup.4 +R.sup.4 C.tbd.CR.sup.5 →W.tbd.CR.sup.5 +R.sup.4 C.tbd.CR.sup.4                                            ( 14)

omitted). The sum of equations 13 and 14 is the catalyzed reaction shown in equation 15. The reaction can run in reverse and

    2R.sup.4 C.tbd.CR.sup.5 →R.sup.4 C.tbd.CR.sup.4 +R.sup.5 C.tbd.CR.sup.5                                            ( 15)

the position of equilibrium which is attained in a closed system depends on the Gibbs free energy of formation of the constituent alkynes. This equilibrium can be displaced by the usual techniques such as removing one of the component alkynes. The alkyne metathesis reaction can be run in neat alkyne or in solvents such as pentane, diethyl ether or toluene, at a temperature from -78° C. to 150° C. The product is recovered by fractional distillation.

The reactions set forth above are conducted in the absence of oxygen and moisture in order to maximize production of product. Typically, the reactions can be conducted in an atmosphere of dry nitrogen or dry inert gas.

The catalysts of this invention are particularly useful for producing acetylenes containing 18 to 20 carbon atoms in the chain which, in turn, are useful as starting materials for making detergents.

SPECIFIC EMBODIMENTS OF THE INVENTION

This invention is further illustrated by the following examples, which should not, however, be construed as fully delineating the scope of this discovery.

In order to avoid the presence of oxygen and moisture, all experiments below were carried out in an atmosphere of dry molecular nitrogen.

Trineopentylneopentylidyne tungsten, (Me₃ CCH₂)₃ W.tbd.CCMe₃, was prepared by reacting six equivalents of neopentyllithium with WCl₆ in ether (Clark and Schrock, J. Am. Chem. Soc., 100, 6774 (1978)).

In the examples below Me=CH₃, Ph=C₆ H₅, Et=C₂ H₅, and tol=para-C₆ H₄ Me.

EXAMPLE I Preparation of [Et₄ N]⁺ [W(CCMe₃)Cl₄ ]⁻

An ether solution of HCl (12 ml, 1 M) was added dropwise at -20° to a stirred dichloromethane solution of W(CCMe₃) (CH₂ CMe₃)₃ (1.88 g, 4 mmol) and Et₄ N⁺ Cl⁻ (0.66 g, 4 mmol). The reaction was warmed to room temperature and the blue precipitate filtered off and recrystallized from dichloromethane at -30°; yield 1.73 g (82%) [Et₄ N]⁺ [W(CCMe₃)Cl₄ ]⁻.

Anal. Calcd for WC₁₃ H₂₉ Cl₄ N: C, 29.74; H, 5.57. Found: c, 30.28; H, 5.69. ¹³ C NMR (ppm, CD₂ Cl₂): 337 (s, CCMe₃), 52.4 (t, NCH₂ CH₃), 45.7 (s, CCMe₃), 33.5 (q, CCMe₃), 7.2 (q, NCH₂ CH₃).

EXAMPLE II Preparation of W(CCMe₃)Cl₃ (OPEt₃)

A solution of W(CCMe₃)(CH₂ CMe₃)₃ (0.50 g, 0.537 mmol) and OPEt₃ (0.14 g, 1.07 mmol) in 10 ml toluene was cooled to -78° C. 2.1 M HCl in ethyl ether (1.67 ml, 3.50 mmol) was added slowly by syringe to this yellow-orange solution. A blue-green color was generated and after 5 minutes, a blue solid precipitated from solution. This solid was collected by filtration and washed with ether; total yield 0.43 g (81%) of W(CCMe₃)Cl₃ (OPEt₃).

¹ H NMR (ppm, CDCl₃, 250 MHz): 2.16 (m, 6, PCH₂ CH₃), 1.31 (m, 9, PCH₂ CH₃), 1.22 (s, 9, CMe₃). ¹³ C NMR (ppm, CDCl₃, gated ¹ H decoupled, 62.8 MHz): 329.3 (s, J_(CW) =209 Hz, CCMe₃), 46.1 (s, CCMe₃), 34.9 (q, J_(CH) =127 Hz, CCMe₃), 17.9 (dt, J_(CP) =66.6 Hz, J_(CH) =124 Hz, OPCH₂ CH₃), 5.6 (q, J_(CH) =124 Hz, OPCH₂ CH₃). ³¹ P{¹ H} NMR (ppm, CDCl₃, 36.2 MHz): 82.4 (s).

EXAMPLE III Preparation of W(CCMe₃)Cl₃ (PMe₃)₃

PMe₃ (1.0 ml, 10.5 mmol) was added by syringe to a solution of W(CCMe₃)Cl₃ (OPEt₃) (1.71 g, 3.46 mmol) in 5 ml tetrahydrofuran. The color of the solution turned from blue to yellow, and after 5 minutes, yellow crystals formed in the solution. This product was collected by filtration and recrystallized from a mixture of dichloromethane and pentane at -30° C.; total yield 1.89 g (93%) W(CCMe₃)Cl₃ (PMe₃)₃. W(CCMe₃)Cl₃ (PMe₃)₃ also can be prepared by adding excess PMe₃ to [NEt₄ ]⁺ [W(CCMe₃)Cl₄ ]⁻.

Anal. Calcd for WC₁₄ H₃₆ Cl₃ P₃ : C, 28.62; H, 6.18. Found: C, 29.08; H, 6.25. ¹ H NMR (ppm, CDCl₃, -20° C., 250 MHz): 1.66 (t, 3, J_(HP) =9.8 Hz, PMe₃), 1.42 (s, 1, CMe₃). ¹³ C NMR (ppm, CDCl₃, -20 ° C., gated ¹ H decoupled, 62.8 MHz): 400.5 (q, J_(CP) =39.7 Hz, CCMe₃), 56.7 (s, CCMe₃), 34.4 (q, J_(CH) =125 Hz, CCMe₃), 18.7 (qq, J_(CP) =11.6 Hz, J_(CH) =137 Hz, PMe₃). ³¹ P{¹ H} NMR (ppm, CDCl₃, -80° C., 36.2 MHz): 19.4 (s, J_(PW) =247 Hz).

EXAMPLE IV Preparation of W(CCMe₃)Cl₃ (PEt₃)(OPEt₃)

PEt₃ (0.25 g, 2.12 mmol) was added to a solution of W(CCMe₃)Cl₃ (OPEt₃) (0.85 g, 1.73 mmol) in 5 ml tetrahydrofuran. The color of the solution changed from blue to green-blue. The reaction mixture was filtered, and the solvent was removed in vacuo to yield oily blue-green crystals. This product was recrystallized from a mixture of ether and pentane to yield 0.95 g (90%) of blue, crystalline W(CCMe₃)Cl₃ (PEt₃)(OPEt₃).

Anal. Calcd for WC₁₇ H₃₉ Cl₃ OP₂ : C, 33.38; H, 6.43.

Found: C, 33.70; H, 6.46. ¹ H NMR (ppm, C₆ D₆, 250 MHz): 1.82 (dq, 2, J_(HH) =7.7 Hz, J_(HP) =8.3 Hz, OPCH₂ CH₃), 1.61 (dq, 2, J_(HH) =7.7 Hz, J_(HP) =6.3 Hz, PCH₂ CH₃), 1.37 (s, 3, CMe₃), 1.00 (tq, 3, J_(HH) =7.4 Hz, J_(HP) =14.7 Hz, OPCH₂ CH₃), 0.88 (tq, 3, J_(HH) =7.4 Hz, J_(HP) =16.9 Hz, OPCH₂ CH₃). ¹³ C NMR (ppm, C₆ D₆, gated ¹ H decoupled, 62.8 MHz): 339.5 (d, J_(CP) =14.5 Hz, CCMe₃), 46.9 (s, CCMe₃), 35.1 (q, J_(CH) =128 Hz, CCMe₃), 19.1 (dt, J_(CP) =58.1 Hz, J_(CH) =128 Hz, OPCH₂ CH₃ ), 18.5 (dt, J_(CP) =23.3 Hz, J_(CH) =131 Hz, OPCH₂ CH₃), 7.2 (q, J_(CH) =125 Hz, PCH₂ CH₃), 5.9 (q, J_(CH) =128 Hz, OPCH₂ CH₃). ³¹ P {¹ H} NMR (ppm, C₆ D₆, 36.2 MHz): 63.9 (s, OPEt₃), 33.2 (s, J_(PW) =256 Hz, PEt₃). IR: ν_(O=P) =1117 cm⁻¹.

EXAMPLE V Preparation of W(CCMe₃)(OCMe₃)₃

[Et₄ N]⁺ [W(CCMe₃)Cl₄ ]⁻ (2.0 g, 3.8 mmol) was added in small portions as a solid to 40 ml of tetrahydrofuran containing 1.28 g (11.4 mmol) KOCMe₃. After addition was complete the reaction mixture was stirred for one hour and filtered through Celite. The solvent was removed in vacuo and the yellow residue was sublimed at 60° (5 μ) to give 1.35 g (75%) W(CCMe₃)(OCMe₃)₃.

¹³ C NMR (ppm, CDCl₃): 271.3 (s, CCMe₃), 78.6 (s, OCMe₃), 49.5 (s, CCMe₃), 33.9 (q, CCMe₃), 32.3 (q, OCMe₃).

EXAMPLE VI Preparation of [Et₄ N]⁺ [W(CCMe₃)(OPh)₄ ]⁻

[Et₄ N]⁺ [W(CCMe₃)Cl₄ ]⁻ (0.52 g, 1 mmol) was added to a solution of tetrahydrofuran containing 0.4 g (4 mmol) LiOPh. The reaction mixture was filtered through Celite and the solvents were removed from the filtrate in vacuo to give a yellow oil which was converted into a microcrystalline yellow powder on addition of ethyl ether; yield ˜80% [Et₄ N]⁺ [W(CCMe₃)(OPh)₄ ]⁻.

¹³ C NMR (ppm, CH₃ CN): 290.3 (s, CCMe₃), 169.2, 128.2, 121.0, 118.5 (phenyl carbon resonances), 52.3 (t, NCH₂ CH₃), 47.7 (s, CCMe₃), 34.1 (q, CCMe₃).

EXAMPLE VII Preparation of W(CPh)Cl₃ (PMe₃)₃

A solution containing W(CCMe₃)(Cl₃)(OPEt₃) (0.43 g, 0.866 mmol) and diphenylacetylene (0.18 g, 1.0 mmol) in 2 ml of tetrahydrofuran was heated to 60° C. for 2 hours. During this time, the color of the reaction mixture changed from blue to green. Phenyl-t-butylacetylene (100% yield versus tungsten) was observed in the reaction mixture by gas chromatography. The reaction mixture was filtered and PMe₃ (0.30 ml, 3.0 mmol) was added by syringe. The color of the solution turned yellow, and after the addition of 2 ml pentane, yellow crystals precipitated from solution. The product was collected by filtration and was recrystallized from a mixture of tetrahydrofuran and pentane at -30° C.; total yield 0.47 g (89%) W(CPh)Cl₃ (PMe₃)₃.

¹ H NMR (ppm, CDCl₃, 250 MHz): 7.38 and 7.09 (m, 5, phenyl proton resonances), 1.56 (s, 27, PMe₃). ¹³ C NMR (ppm, CDCl₃, gated ¹ H decoupled, 62.8 MHz): 356.8 (q, J_(CP) =43.6 Hz, CPh), 148.0, 128.1, and 126.5 (phenyl carbon resonances), 16.5 (qq, J_(CP) =11.6 Hz, J_(CH) =128 Hz, PMe₃). ³¹ P{¹ H} NMR (ppm, CDCl₃, 36.2 MHz): 16.7 (s, J_(PW) =224 Hz).

EXAMPLE VIII Preparation of W(CPh)Cl₃ (PEt₃)(OPEt₃)

A solution of W(CCMe₃)Cl₃ (OPEt₃) (0.43 g, 0.866 mmol) and diphenylacetylene (0.18 g, 1.0 mmol) in 2 ml of tetrahydrofuran was heated to 60° C. for 2 h. The color of the reaction mixture changed from blue to green. Phenyl-t-butylacetylene (100%) was observed in the reaction by gas chromatography. The reaction mixture was filtered and PEt₃ (0.12 g, 1.0 mmol) was added. The reaction mixture was again filtered, and all volatiles removed in vacuo to yield a green oil. This oil was dissolved in a minimal amount of ether, and an equal volume of pentane was added. Blue-green crystals precipitated from this solution at -30° C.; total yield 0.44 g (80%) W(CPh)Cl₃ (PEt₃)(OPEt₃).

¹ H NMR (ppm, C₆ D₆, 250 MHz): 7.47, 6.90, and 6.67 (m, 5, J_(HH) =7.4 Hz, phenyl proton resonances), 2.00 (m, 12, PCH₂ CH₃ and OPCH₂ CH₃), 1.21 (dt, 9, J_(HH) =6.6 Hz, J_(HP) =17.7 Hz, OPCH₂ CH₃), 1.11 (dt, 9, J_(HH) =7.4 Hz, J_(HP) =15.1 Hz, PCH₂ CH₃). ¹³ C NMR (ppm, C₆ D₆, gated ¹ H decoupled, 62.8 MHz): 321.9 (bs, CPh), 138.6, 137.8, 129.7, and 124.8 (m, phenyl carbon resonances), 17.9 (dt, J_(CP) =66.9 Hz, J_(CH) =125 Hz, OPCH₂ CH₃), 17.1 (dt, J_(CP) =26.2 Hz, J_(CH) =125 Hz, PCH₂ CH₃), 6.9 (q, J_(CH) =128 Hz, PCH₂ CH₃), 4.8 (q, J.sub. CH =128 Hz, OPCH₂ CH₃). ³¹ P{¹ H} NMR (ppm, C₆ D₆, 36.2 MHz): 66.3 (s, OPEt₃), 39.1 (s, J_(PW) =256 Hz, PEt₃). IR: ν_(O=P) =1124 cm⁻¹.

EXAMPLE IX Preparation of W(CPh)(OCMe₃)₃

Diphenylacetylene (0.36 g, 2 mmol) was added to a pentane solution (5 ml) of W(CCMe₃)(OCMe₃)₃. After three hours the volatiles were removed from the reaction in vacuo and the residue was sublimed at 80° C. (2μ); yield 80% of yellow W(CPh)(OCMe₃)₃.

¹³ C NMR (ppm, CDCl₃): 257.2 (s, CPh), 147.6, 128, 127, 125 (phenyl carbon resonances), 80.8 (s, OCMe₃), 32.4 (q, OCMe₃).

EXAMPLE X Metathesis of 3-heptyne by W(CCMe₃)(OCMe₃)₃

W(CCMe₃)(OCMe₃)₃ (50 mg) was added to 13.0 g of 3-heptyne at 25°. After one minute the reaction mixture was passed down a column of activated alumina to remove the catalyst. The colorless effluent consisted of 13.0 g of a 1:2:1 mixture of 3-hexyne, 3-heptyne, and 4-octyne, respectively, by quantitative gas chromatographic analysis and comparison with authentic samples. It contained the expected amount of equal parts Me₃ CC.tbd.CEt and Me₃ CC.tbd.CPr by gas chromatography. A mixture of W(CPr)(OCMe₃)₃ and W(CEt)(OCMe₃)₃ could be observed by ¹³ C NMR after removing all volatiles in vacuo from a reaction mixture.

EXAMPLE XI Metathesis of phenyltolylacetylene by W(CCMe₃)(OCMe₃)₃

Phenyltolylacetylene (2.50 g) was dissolved in toluene and 41 mg of W(CCMe₃)(OCMe₃)₃ (0.075 mmol) was added. After one hour the solution contained 0.037 mmol of Me₃ CC.tbd.CPh, 0.037 mmol of Me₃ CC.tbd.Ctol, and 2.50 g of a 1:2:1 mixture of diphenylacetylene, phenyltolylacetylene, and ditolylacetylene, respectively. A mixture of W(CPh)(OCMe₃)₃ and W(Ctol)(OCMe₃)₃ could be observed in the reaction mixture by ¹³ C NMR.

EXAMPLE XII Metathesis of phenyltolylacetylene by W(CCMe₃)Cl₃ (OPEt₃)

Phenyltolylacetylene (3.5 g) was added to a solution of W(CCMe₃)Cl₃ (OPEt₃) (0.17 mmol) in 2 ml of tetrahydrofuran. After heating the reaction at 60° for two hours a 1:2:1 mixture of diphenylacetylene, phenyltolylacetylene, and ditolylacetylene was generated. 

I claim:
 1. A compound of the formula

    [L.sub.Y X.sub.n+3 W.tbd.CR.sup.3 ].sup.n- (M.sup.+).sup.n

wherein R³ is an alkyl or aryl; L is a moiety of the formula ZR⁴ R⁵ R⁶ wherein Z is selected from the group consisting of nitrogen and phosphorous and R⁴, R⁵ and R⁶ can be the same or different and are alkyl, aralkyl or aryl; L is a moiety of the formula OZR⁴ R⁵ R⁶, ZR⁴ R⁵ R⁶, ZR⁴ R⁵ (OR⁶), ZR⁴ (OR⁵)(OR⁶) or Z(OR⁴)(OR⁵)(OR⁶); X is F, Cl, Br, I, OR⁴, NR⁴ R⁵ or SR⁴ ; M⁺ is selected from the group consisting of [NR R³ R⁴ R⁵ R⁶ ]⁺, [PR³ R⁴ R⁵ R⁶ ]⁺, li⁺, K⁺ or Na⁺ ; alkyl has 1-10 carbons, aralkyl has 7-10 carbons and aryl has 6-10 carbons; n is 0 or 1; y is 0, 1 or 2;with the proviso that y is 0 when X is OR⁴, NR⁴ R⁵ or SR⁴, and n=0; y is 0 when X is OR⁴, F, Cl, Br or 1, and n=1.
 2. The compound of the formula [Et₄ N]⁺ [W(CCMe₃)Cl₄ ]⁻.
 3. The compound of the formula W(CCMe₃)Cl₃ (OPEt₃).
 4. The compound of the formula W(CCMe₃)Cl₃ (PMe₃)₃.
 5. The compound of the formula W(CCMe₃)Cl₃ (PEt₃)(OPEt₃).
 6. The compound of the formula W(CCMe₃)(OCMe₃)₃.
 7. The compound of the formula [Et₄ N]⁺ [W(CCMe₃)(OPh)₄ ]⁻.
 8. The compound of the formula W(CPh)Cl₃ (PMe₃)₃.
 9. The compound of the formula W(CPh)Cl₃ (PEt₃)(OPEt₃).
 10. The compound of the formula W(CPh)(OCMe₃)₃. 